CN102726377B - Controlled release compositions - Google Patents

Controlled release compositions Download PDF

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CN102726377B
CN102726377B CN201210103039.7A CN201210103039A CN102726377B CN 102726377 B CN102726377 B CN 102726377B CN 201210103039 A CN201210103039 A CN 201210103039A CN 102726377 B CN102726377 B CN 102726377B
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compound
composition
equal
matrix
cyclopropene
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CN102726377A (en
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R·M·雅各布森
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Rohm and Haas Co
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    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
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    • C08L101/00Compositions of unspecified macromolecular compounds
    • AHUMAN NECESSITIES
    • A01AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
    • A01NPRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
    • A01N27/00Biocides, pest repellants or attractants, or plant growth regulators containing hydrocarbons
    • AHUMAN NECESSITIES
    • A61MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61KPREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00Medicinal preparations characterised by special physical form
    • A61K9/20Pills, tablets, discs, rods
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08KUse of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K9/00Use of pretreated ingredients
    • C08K9/10Encapsulated ingredients

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Abstract

A composition comprising (a) a meltable solid matrix comprising (i) one or more solid hydrophobic substance, and (ii) one or more solid hydrophilic substance, and (b) distributed in said matrix, one or more encapsulation complex of a volatile cyclopropene compound encapsulated in a molecular encapsulation agent. Also provided is a method of treating plants or plant parts comprising placing said plants or plant parts and the composition of claim 1 into a container and allowing said plants or plant parts and said composition of claim 1 to remain together in said container for 1 day or longer.

Description

The composition of controlled release
Background technology
There is various problems in the compound of processing volatilization.A kind of to make method that volatile compound is easily processed be to form a kind of molecule to seal compound (complex), wherein the molecule of volatile compound described in molecule encapsulant encapsulates.In some cases, it is powder type that described molecule is sealed compound, can be optionally and other solid particle blending of other material, form the powder of blending.This powder is conventionally compared more easily and is stored, transports and/or use with pure volatile compound.
Wish to use while being included in the volatile compound in this powder, a kind of method of routine comprises described powder contacted with discharging compound, and this release compound can promote or make described volatile compound to seal compound and discharge from molecule when sealing compound and contact.For some useful molecules, seal compound, water is a kind of release compound.
But, provide the molecule of powder type to seal compound and can not solve all problems relevant to using volatile compound.For example, while using release compound to discharge volatile compound from this powder, contacting between described powder and described release compound may be not tight, and the release of described volatile compound may be not exclusively or undesirably slowly or simultaneously had two kinds of situations.In this case, the release that may must take some measures to improve described volatile compound, for example, wait for that undesirable volatile compound that allows for a long time discharges; Some mechanical assistants (such as shake, stir, force gas to enter in water to produce bubble etc.) are provided; Or to described powder, provide the additive that produces effervescent effect while contacting with water.United States Patent (USP) the 6th, has described a kind of composition 426, No. 319, and the molecule that it comprises compound cyclopropene and molecule encapsulation agent is sealed compound, and this molecule is sealed compound and mixed with water absorbing material.
In many cases, when the composition that comprises volatile compound contacts with release compound, wish that volatile compound progressively discharges.But, similar United States Patent (USP) the 6th, the relative compound cyclopropene that promptly discharges the conventionally when composition in 426, No. 319 contacts with water vapour.
Be desirable to provide a kind of composition, it is sealed and progressively discharges satisfactorily useful volatile compound when including the volatile compound of use in compound and contacting with aqueous water or water vapour at molecule.
Summary of the invention
It is below content of the present invention.
First aspect of the present invention is a kind of composition, and it comprises (a) meltability solid matrix, and described meltability solid matrix comprises (i) one or more solid hydrophobic materials and (ii) one or more solid hydrophilic materials; (b) one or more that are encapsulated in volatility compound cyclopropene in molecule encapsulation agent are sealed compound, described in seal compound and be distributed in described matrix.
Another aspect of the present invention is a kind of method of processing plant or plant part, it comprises the described composition of described plant or plant part and first aspect of the present invention is placed in container, and described plant or plant part is kept 1 day together with composition as claimed in claim 1 in described container or the longer time.
Embodiment
It is below detailed description of the present invention.
In this article, unless context clearly has different explanations, following term has limited implication.
In this article, " hydrocarbon " represents the chemical group or the compound that in its atom, comprise one or more carbon atoms, one or more hydrogen atom and do not comprise other atom.
In this article, " matrix " be solid and there is successional material.In the macroscopic sample of the composition that comprises matrix, described matrix forms continuous three-dimensional body (body).Described matrix can connect the whole surface of sample; If do not connect the whole surface of sample, it will connect a plurality of positions on the surface of sample.At least 50% of the whole surface area of sample is connected with matrix.Described matrix can be the mixture of a kind of pure material or two or more materials.
Macroscopic sample is that volume is at least the main body that 1 cubic centimetre and minor axis are more than or equal to 3mm.Axle is to be positioned at the line segment in body surfaces by described main quality center (the center of mass) and end points.
If described matrix is mixture, the one-tenth branch in mixture forms solution or dispersion or their combination.In solution, described composition is miscible each other; That is, they can dissolve (on molecular level, closely mixing) mutually.In dispersion, a kind of composition (or solution of composition) exists with continuous phase form, and one or more other compositions exist to be distributed in the form of described continuous phase granule (diameter is less than or equal to 1 millimeter) everywhere.
Particle (no matter be powder type or be dispersed in matrix) characterizes with its diameter.If fruit granule is not spherical, think that the diameter of described particle is the diameter of the ball identical with described particle volume herein.
In this article, if material is solid state in certain temperature range (at least comprising 0-40 ℃), think that this material is solid.For example, solid comprises crystalline solid, unbodied glassy solids, waxy solid and rubber-like solid.Macroscopic solid sample does not have perceptible distortion under himself weight.Be of a size of the cube solid material of 1cm * 1cm * 1cm; In 25 ℃, place 7 days on smooth surface, it highly at least keeps 95%.
In this article, if a kind of material be solid defined above and its fusing point or softening point higher than 40 ℃ and lower than 120 ℃, think that this material is meltability solid.Described softening point is the temperature being in a liquid state higher than this material temperature, or material enough soft (if not being in a liquid state) can by plant equipment, for example agitator, extruder or kneader carry out blending or the temperature of knead (masticate).
Herein, if the boiling point of compound is less than or equal to 100 ℃ under an atmospheric pressure, this compound is volatile.
In this article, lyophobic dust is the material that meets following one or more following hydrophobicity standards.The first hydrophobicity standard is water contact angle.If the contact angle of a kind of clean surface of material and water droplet is more than or equal to 90 °, this material is hydrophobic.Described contact angle is measured according to D7334-08 method of testing (Pennsylvania, America Xikang She Huoken, international ASTM (ASTM International, West Conshohocken, PA, USA)).
The second hydrophobicity standard is to form.If material is pure lyophobic dust or a hydrophobicity mixture, this material is hydrophobic.Hydrophobicity mixture comprises one or more pure lyophobic dusts, and in mixture, the amount of all pure lyophobic dusts is more than or equal to 75 % by weight, and the weight of described mixture of take is benchmark.If the molecule of material has one or more fat groups, and its solvability of 25 ℃ in water is less than the 1 % by weight weight of water (take be benchmark), and this material is pure lyophobic dust.Fat group is with lower a kind of: (1) aliphatic group, and it has 8 or more carbon atom; Only there is hydrogen atom and carbon atom; It is straight chain, side chain, ring-type or their combination; (2) chemical group of classification (1), wherein one or more hydrogen atoms are replaced by halogen atom; Or (3) silicone group.Silicone group is the group of the linear chain that comprises 5 or more siloxane groups.Siloxane group has following structure (I):
Each R wherein sbe independent of other R s, be hydrogen, there is the hydrocarbyl group or another siloxane group that are less than or equal to 6 carbon atoms.
The third hydrophobicity standard is water imbibition.Lyophobic dust is at 25 ℃ during the air balance with 100% relative moisture, and described lyophobic dust absorbs a certain amount of water from air, so that the weight of the water absorbing is less than or equal to 0.0001 divided by the business of the dry weight of lyophobic dust.
The 4th kind of hydrophobicity standard is water vapour permeability.While testing the hydrophobic material film of 40 micron thickness under 37.8 ℃ and 90% relative moisture, its water vapour permeability is less than every square metre of 25 grams of water vapour film every day.
The 5th kind of hydrophobicity standard is as follows: if the amount of vinyl acetate is less than the 20 % by weight weight of copolymer (take be benchmark) in the copolymer of ethene and vinyl acetate, the polymer of the copolymer of ethene and vinyl acetate is hydrophobic.
In this article, hydroaropic substance is the material that meets following one or both hydrophily standards.The first hydrophily standard is water imbibition: when hydroaropic substance is at 25 ℃ during the air balance with 100% relative moisture, described hydroaropic substance absorbs a certain amount of water from air, so that the weight of the water absorbing is more than or equal to 0.001 divided by the business of the dry weight of hydroaropic substance.
The second hydrophily standard is water vapour permeability.While testing the hydrophilic material film of 40 micron thickness under 37.8 ℃ and 90% relative moisture, its water vapour permeability is greater than every square metre of 50 grams of water vapour film every day.
The third hydrophily standard is as follows: if the amount of vinyl acetate is more than or equal to the 20 % by weight weight of copolymer (take be benchmark) in the copolymer of ethene and vinyl acetate, the polymer of the copolymer of ethene and vinyl acetate is hydrophilic.
In this article, wetting agent is while contacting with the air of 100% relative moisture at 25 ℃, can from air, absorb the material of water.When wetting agent is when at 25 ℃, the air with 100% relative moisture reaches balance, the business that the weight of the water that wetting agent absorbs obtains divided by the dry weight of described wetting agent is more than or equal to 0.1.Some wetting agents are hygroscopy materials.At 25 ℃, can from air, absorb enough water with the hygroscopy material of the air balance of 100% relative moisture, in water, form the liquid solution of hygroscopy material.
In this article, water imbibition material is the solid material that has hole, passage or have other cavity of capturing hydrone ability.The molecule of water imbibition material is swelling or contrary to existing the hydrone absorbing to rearrange not.Before contacting with water, described cavity is empty (being that each cavity only comprises air or vacuum).Enter this cavity and keep there the hydrone of limited a period of time to be called as in this article the water of " absorption ".
When molecule encapsulant encapsulates compound or compound a part of, being combined in of obtaining is called as molecule herein and seals compound.
In this article, " polymer " is as FW Billmeyer, JR. at < < polymer science textbook (Textbook ofPolymer Science) > > (second edition, 1971) in, define the larger molecule that the product of the less chemical repeat unit of serving as reasons forms.The structure of polymer can be combinations that are line style, branching, star, ring-type, high branching, crosslinked or these situations; Polymer can comprise the repetitive (" homopolymers ") of single type, or can comprise the repetitive (" copolymer ") more than a type.Various repetitives in copolymer can with random, sequentially, block and other form arrange, or can arrange with any mixing of these forms or the form of combination.Become the compound of repetitive in polymer with the reaction of identical and/or not identical compound and be called as in this article " monomer ".The repetitive obtaining from this reaction is called as this monomer " residue " in this article.
Polymer molecular weight can be measured by standard method, for example, adopt SEC (SEC, also referred to as gel permeation chromatography or GPC).The number-average molecular weight of polymer (Mw) is equal to or greater than 500.
If some polymer chains or all polymer chain are side chains, polymer is cross-linked.If the branching existing in polymer is enough to affect physical property and the polymer of polymer, have limited molecular weight, this polymer is lightly crosslinked.If the branching existing in polymer is enough to by percolation threshold (percolationthreshold), this polymer is cross-linked completely.Completely crosslinked polymer is insoluble to any solvent, even the solvent of the same linear polymer forming of solubilized.It is said that completely crosslinked polymer has unlimited molecular weight.
Useful sign of composition is solids content.The solids content of composition is determined in the following manner: prepare the composition layer that thickness is less than or equal to 1 millimeter, make volatile compound leave composition, for example, this layer is placed in the stove of circulating air of 100 ℃ to 1 hour.The weight that volatile matter leaves rear retained material is solids content divided by the original weight of composition, is expressed as a percentage.
The present invention includes the purposes of one or more compound cyclopropenes.In this article, compound cyclopropene is any compound with following structural formula:
R wherein 1, R 2, R 3and R 4be selected from independently of one another the chemical group shown in H and following formula:
-(L) n-Z
Wherein n is the integer of 0-12.Each divalent group naturally of L.Suitable L group comprises the group that for example comprises the one or more atoms that are selected from lower group: H, B, C, N, O, P, S, Si or their combination.Atom in L group can be connected to each other by singly-bound, two key, triple bond or their combination.Each L group can be straight chain, side chain, ring-type or its combination.In any one R group, (be R 1, R 2, R 3and R 4in any), hetero atom (i.e. atom except H and C) add up to 0-6.
Independently, in any one R group, the sum of non-hydrogen atom is equal to or less than 50.
Each univalent perssad naturally of Z.Z is selected from lower group independently of one another: hydrogen, halogen, cyano group, nitro, nitroso, azido, chloric acid ester group, bromic acid ester group, acid iodide ester group, isocyanate group (isocyanato), isonitrile base (isocyanido), isothiocyanic acid base (isothiocyanato), five fluorine sulfenyls and chemical group G, wherein G is the member ring systems of 3-14 unit.
R 1, R 2, R 3and R 4group is independently selected from suitable group.R 1, R 2, R 3and R 4group can be identical, or in the middle of them, the group of any amount can be different from all the other groups.Be suitable as R 1, R 2, R 3and R 4in one or more group can directly be connected with cyclopropylene ring, or be connected with cyclopropylene ring via middle group, described in the middle of group be for example containing heteroatomic group.
In this article, if one or more hydrogen atoms of certain chemical group are substituted base while replacing, certain chemical group be known as " substituted ".Suitable substituting group for example comprises: alkyl, thiazolinyl, acetylamino, alkoxyl, alkoxyl alkoxyl, alkoxy carbonyl, Alkoximino (alkoxyimio), carboxyl, halogen, halogenated alkoxy, hydroxyl, alkyl sulphonyl, alkylthio group, trialkylsilkl, dialkyl amido and their combination.
Suitable R 1, R 2, R 3and R 4group comprises in following group for example any one replacement and unsubstituted form: aliphatic group, aliphatic series oxygen base, alkyl-carbonyl, alkyl phosphonic acid ester group, alkyl phosphoric acid ester group, alkyl amino, alkyl sulphonyl, alkyl carboxyl, alkyl amino sulfonyl, naphthene sulfamide base, cycloalkyl amino, heterocyclic radical (comprising at least one heteroatomic aromatics or non-aromatic cyclic group in ring), aryl, hydrogen, fluorine, chlorine, bromine, iodine, cyano group, nitro, nitroso, azido, chloric acid ester group (chlorato), bromic acid ester group (bromato), acid iodide ester group (iodato), isocyanate group (isocyanato), isonitrile base (isocyanido), isothiocyanic acid base (isothiocyanato), five fluorine sulfenyls (pentafluorothio), acetoxyl group, carbonyl ethyoxyl, cyanic acid base (cyanato), nitrato, nitrito-, perchloric acid ester group (perchlorato), allene base (allenyl), butyl sulfydryl, diethyl phosphonate base (diethylphosphonato), 3,5-dimethylphenyl silicyl, isoquinolyl, sulfydryl, naphthyl, phenoxy group, phenyl, piperidino, pyridine radicals, quinolyl, triethylsilyl and trimethyl silyl.
Suitable R 1, R 2, R 3and R 4group be comprise one or more ionogenic substituent those.These ionogenic groups can or be salt form in unionization form.
Also considered in some embodiments R 3and R 4be combined into independent group, this independent group is connected with No. 3 carbon atoms of described cyclopropylene ring by two keys.Some such compounds are described in United States Patent (USP) discloses No. 2005/0288189.
In a preferred embodiment, use one or more compound cyclopropenes, wherein each R 1, R 2, R 3and R 4hydrogen independently, or replacement or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl; When there is substituting group, described substituting group is halogen, alkoxyl or replacement or unsubstituted phenoxy group independently.In preferred embodiment, each R 1, R 2, R 3and R 4in one or more be hydrogen, be not each R of hydrogen 1, R 2, R 3and R 4replacement or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl independently; When there is substituting group, described substituting group is halogen, alkoxyl or replacement or unsubstituted phenoxy group independently.In preferred embodiment, R 2, R 3and R 4each is hydrogen naturally, R 1hydrogen or unsubstituted alkyl, thiazolinyl, alkynyl, cycloalkyl, cycloalkyl-alkyl, phenyl or naphthyl independently.
In a preferred embodiment, use one or more compound cyclopropenes, wherein R 1, R 2, R 3and R 4in one or more be hydrogen, be not the R of hydrogen 1, R 2, R 3and R 4each is (C1-C4) alkyl naturally.In preferred embodiment, R 1(C 1-C 4) alkyl, R 2, R 3and R 4the hydrogen of respectively doing for oneself.In preferred embodiment, R 1for methyl, R 2, R 3and R 4the hydrogen of respectively doing for oneself, in this article, is called compound cyclopropene " 1-MCP ".
In a preferred embodiment, the boiling point of the compound cyclopropene of use under an atmospheric pressure is equal to or less than 25 ℃; Or be equal to or less than 15 ℃.Independently, in a preferred embodiment, the boiling point of the compound cyclopropene of use under an atmospheric pressure is equal to or higher than-100 ℃; Preferably be equal to or higher than-50 ℃; More preferably be equal to or higher than-25 ℃; More preferably be equal to or higher than 0 ℃.
Composition of the present invention comprises at least one molecule encapsulation agent, a part for described one or more compound cyclopropenes of molecule encapsulant encapsulates or one or more compound cyclopropenes.The compound of a part that comprises compound cyclopropene molecule in the molecule that is encapsulated in molecule encapsulation agent or compound cyclopropene molecule is called as " compound cyclopropene compound " in this article.
In a preferred embodiment, at least one compound cyclopropene compound is inclusion complex (inclusioncomplex).In such inclusion complex, described molecule encapsulation agent forms cavity, and a part for described compound cyclopropene or compound cyclopropene is within this cavity.
Preferably, in such inclusion complex, the cavity inside of described molecule encapsulation agent is nonpolar or inconsistent or meet both of these case with water substantially simultaneously, described compound cyclopropene (or be positioned at the compound cyclopropene within described cavity a part) is also substantially nonpolar or inconsistent with water, or meets both of these case simultaneously.Although the invention is not restricted to theory or the mechanism of any specific, but expection is in so nonpolar compound cyclopropene compound, Van der Waals force, or with the inconsistent interaction of water, or these two kinds of active forces make compound cyclopropene molecule or its part keep the quite a long time within the cavity of molecule encapsulation agent.
The amount of molecule encapsulation agent can be effectively characterizes with the business (" Q1 ") that the molal quantity of molecule encapsulation agent obtains divided by the molal quantity of compound cyclopropene.In a preferred embodiment, Q1 is more than or equal to 0.1; Preferably greater than or equal to 0.2; More preferably greater than or equal 0.5; More preferably greater than or equal 0.9.Independently, in a preferred embodiment, Q1 is less than or equal to 10; Preferably be less than or equal to 5; Be more preferably less than or equal 2; Be more preferably less than or equal 1.5.
Suitable molecule encapsulation agent comprises for example organic and inorganic molecule encapsulation agent.Preferably organic molecule encapsulation agent, comprises the cyclodextrin, unsubstituted cyclodextrin and the crown ether that for example replace.Suitable inorganic molecule encapsulation agent comprises for example zeolite.The mixture of suitable molecule encapsulation agent is also suitable.In a preferred embodiment, described encapsulation agent is alpha-cyclodextrin, beta-schardinger dextrin-, gamma-cyclodextrin or its mixture.In the preferred embodiment of the present invention, use alpha-cyclodextrin.
The present invention relates to the application of (being also called " lyophobic dust (i) " or " material (i) " herein) of one or more solid hydrophobic materials (i).Preferred lyophobic dust (i) is fatty compound, chloroflo, olefin polymer and their mixture.
Fatty compound is the compound with one or more fat-based.Fatty compound comprises for example fatty acid, fat oil, its modified form and their mixture.Suitable modification comprises any method, comprises and can change the chemical reaction that fatty compound forms, as long as the compound obtaining still meets the definition of fatty compound.For example, modification comprise hydrogenation, esterification, trans-ester, deesterify, polymerization, in conjunction with functional group and their combination.Fatty acid has formula R-COOH, and wherein R comprises fat group.Fat oil is the fatty compound that comprises one or more ester groups, hydroxyl, aldehyde radical, ketone group or its combination.
Preferably comprise the fatty acid that at least one has the fat group of 12 or more carbon atoms.More preferably comprise the fatty acid that at least one has the fat group of 16 or more carbon atoms; More preferably comprise the fatty acid that at least one has the fat group of 18 or more carbon atoms.Preferred fatty acid is to comprise the fatty acid that at least one has the fat group that is less than or equal to 22 carbon atoms.Preferred fatty acid comprises at least one for the fat group of saturated hydrocarbyl (, in this group, the key between carbon atom is all singly-bound).In fatty acid, more preferably stearic acid, palmitic acid and their mixture.In fatty acid, more preferably double pressed stearic acid (double pressedstearic acid), it is a kind of fatty acid mixt, and the weight of described double pressed stearic acid of take is benchmark, and wherein the mixture of stearic acid and palmitic acid accounts for 93-100 % by weight.
Suitable lyophobic dust is fat oil.Preferred fat oil is triglycerides.Triglycerides is glycerine and three three esters that fatty acid forms.Preferred triglycerides is hydrogenated vegetable oil.
Chloroflo is the hydrocarbon compound with 12-120 carbon atom.Hydrocarbon molecule in chloroflo can be straight chain, side chain, non-aromatic ring or their combination.Chloroflo exists with the form of two or more different hydrocarbon molecule mixtures conventionally.Chloroflo comprises pertroleum wax, and it can be separated from petroleum crude oil (crude petroleum).Pertroleum wax comprises paraffin, micro-crystallization wax and vaseline.The weight of paraffin of take is benchmark, and paraffin has the straight-chain hydrocarbons that is more than or equal to 60 % by weight, and in paraffin, most straight-chain hydrocarbons has 18-45 carbon atom conventionally separately.Micro-crystallization wax and paraffin phase ratio, the ratio of its branched-chain hydrocarbons and cyclic hydrocarbon is higher.Vaseline is a kind of and micro-crystallization wax mineral oil blending.Preferred micro-crystallization wax in chloroflo.
Olefin polymer is that to take the weight of described olefin polymer be benchmark, and repetitive is the polymer of one or more ethylenic unsaturated hydrocarbon monomer residues of 60-100 % by weight.Any olefin polymer that meets lyophobic dust (i) definition is all suitable as lyophobic dust (i).In olefin polymer, repetitive is that any olefin polymer of 100% one or more ethylenic unsaturated hydrocarbon monomer residues is all suitable as lyophobic dust (i).Polyolefin-wax is also suitable as lyophobic dust (i), and described polyolefin-wax is that number-average molecular weight is less than or equal to 20,000 full olefin polymer.
Olefin polymer also comprises olefin copolymer, and it is that one or more repetitives are olefin polymers of non-hydrocarbon monomer residue.Nonhydrocarbon and can be called as in this article with the monomer of one or more ethylenic unsaturated hydrocarbon monomer copolymerization " alkene-compatibility comonomer ".Suitable alkene-compatibility comonomer comprises, for example acrylic acid, methacrylic acid, alkyl acrylate or alkyl methacrylate and vinyl acetate.Preferably the olefin copolymer as lyophobic dust (i) is to meet the ethene of hydrophobicity standard defined herein and the copolymer of vinyl acetate (" EVA copolymer ").Some are preferably that to take the weight of EVA copolymer be benchmark as olefin copolymers of lyophobic dust (i), and wherein the amount of vinyl acetate residue is the EVA copolymer of 21-40 % by weight.
In a preferred embodiment, composition of the present invention comprises the lyophobic dust that one or more are meltability solids (i).In meltability solid hydrophobic material, preferably fusing point or softening point are more than or equal to the meltability solid hydrophobic material of 50 ℃, more preferably greater than or equal the meltability solid hydrophobic material of 60 ℃.In meltability solid hydrophobic material, preferably fusing point or softening point are less than or equal to the meltability solid hydrophobic material of 110 ℃, are more preferably less than or equal the meltability solid hydrophobic material of 80 ℃.
Preferred lyophobic dust (i) comprises fatty compound, chloroflo and composition thereof and other optional composition.Preferred lyophobic dust (i) comprises fatty acid, fat oil, chloroflo and composition thereof and other optional composition.Preferred lyophobic dust (i) comprises double pressed stearic acid, hydrogenated vegetable oil, micro-crystallization wax and composition thereof and other optional composition.
The present invention relates to the application of one or more hydroaropic substances (ii) (herein also referred to as " hydroaropic substance (ii) " or " material (ii) ").Preferred hydroaropic substance (ii) is polymer.Preferably for the polymer of hydroaropic substance (ii), comprise cellulose, polyethylene glycol, hydrophilic ethylene-vinyl acetate copolymer and containing the polymer of side joint amine groups.
The polymer that cellulose is comprised of the repetitive of D-Glucose.Preferred cellulose is native cellulose, avicel cellulose and their mixture.
The polymer that polyethylene glycol is comprised of the repetitive of oxirane:
-(CH 2-CH 2-O)-。
The preferred polyethylene glycol as hydroaropic substance (ii) is that number-average molecular weight is less than or equal to 20,000 polyethylene glycol; More preferably number-average molecular weight is less than or equal to 10,000 polyethylene glycol.The preferred polyethylene glycol as hydroaropic substance (ii) is that number-average molecular weight is more than or equal to 3,000 polyethylene glycol; More preferably number-average molecular weight is more than or equal to 5,000 polyethylene glycol.
Containing the polymer of side joint amide group, be that the residue that is wherein the more than or equal to 50 % by weight weight of the described polymer containing side joint amide group (take be benchmark) has the chemical group with described main polymer chain side joint, this side joint chemical group is connected with main polymer chain by one or more covalent bonds, and described side joint chemical group has amide group (it can be whole side joint chemical groups or part side joint chemical group).Amide groups can be primary amide base, secondary amide base or teritary amide base.Preferred side joint chemical group is 2-Pyrrolidone base, preferably has the nitrogen-atoms being connected with carbon atom on main polymer chain by covalent bond.Preferred containing in the polymer of side joint amide group, preferred PVP polymer, in this polymer, polymeric residues is the NVP residue that the is more than or equal to 35 % by weight weight of described PVP polymer (take be benchmark).Preferred PVP polymer is crosslinked PVP polymer.
Preferred hydroaropic substance (ii) comprises a kind of in following material, and optionally contain other composition: (A) one or more number-average molecular weights are greater than 3, 000 polyethylene glycol, (B) one or more number-average molecular weights are greater than 3, 000 polyethylene glycol and one or more cellulosic one or more mixtures, (C) one or more hydrophilic ethylene-vinyl acetate copolymers, (D) one or more mixtures of one or more hydrophilic ethylene-vinyl acetate copolymers and one or more cross-linked pvps, or (E) one or more hydrophilic ethylene-vinyl acetate copolymers and one or more cellulosic one or more mixtures.
Some hydroaropic substances (ii) that use are in the present invention the hydroaropic substances that is similarly meltability solid.In meltability solid hydrophilic material, preferably fusing point or softening point are more than or equal to the meltability solid hydrophilic material of 50 ℃, more preferably greater than or equal the meltability solid hydrophilic material of 60 ℃.In meltability solid hydrophilic material, preferably fusing point or softening point are less than or equal to the meltability solid hydrophilic material of 110 ℃, be more preferably less than or equal the meltability solid hydrophilic material of 90 ℃, be more preferably less than or equal the meltability solid hydrophilic material of 80 ℃.
Composition of the present invention comprises meltability matrix, and described meltability matrix comprises one or more lyophobic dusts (i) and one or more hydroaropic substances (ii).In some embodiments, described matrix is the solution of all lyophobic dusts (i) and all hydroaropic substances (ii).I.e. all materials (i) and (ii) can dissolve fully each other, the mixture obtaining is like this solution.
In a preferred embodiment, the fusing point of described meltability matrix is greater than 40 ℃ and be less than 120 ℃.The fusing point of matrix is preferably greater than or equal to 50 ℃; More preferably greater than or equal 60 ℃.The fusing point of matrix is preferably less than or equal to 110 ℃, is more preferably less than or equals 90 ℃, is more preferably less than or equals 80 ℃.(shear rate is 1 second can to characterize the viscosity of matrix with " pour point scope (pour range) " -1), pour point scope is higher than the temperature to 125 of 3 ℃ of fusing points ℃ with higher than lower temperature among the temperature of 25 ℃ of fusing points.Preferably, the viscosity in matrix described in described pour point scope is less than or equal to 3,000 milli handkerchiefs second (3,000 centipoise); Be more preferably less than or equal 1,000 milli handkerchief second (1,000 centipoise); Be more preferably less than or equal 5,00 milli handkerchiefs second (500 centipoise).
In some embodiments (" dispersion embodiment "), in matrix, one or more materials (i) or one or more materials (ii) are present in the dispersion of described matrix continuous phase with particle form.In disperseing embodiment, the continuous phase of described matrix comprises one or more lyophobic dusts (i).The business (" Q2 ") that the weight summation of all lyophobic dusts (i) that the amount of lyophobic dust in the continuous phase of described matrix (i) comprises in described matrix continuous phase obtains divided by the gross weight of described matrix continuous phase characterizes.Preferably, Q2 is more than or equal to 0.2, more preferably greater than or equal 0.3.
The preferred composition of the present invention comprises one or more wetting agents.Preferred wetting agent is potassium acetate and polyethylene glycol.Polyethylene glycol preferred number average molecular weight as wetting agent is less than or equal to 3,000; Be more preferably less than or equal 2,000.Polyethylene glycol preferred number average molecular weight as wetting agent is more than or equal to 500.While there is at least one meltability solid hydrophilic material (ii) of non-polyethylene glycol in composition, think that in this article polyethylene glycol can be used as wetting agent.
In some embodiments, in composition, can there are one or more other materials.This other material can not be used as lyophobic dust (i) or hydroaropic substance (ii) or be encapsulated in the volatility compound cyclopropene in molecule encapsulation agent.Some other materials can be hydrophobicitys or hydrophilic, but are not meltability solids.Other suitable material comprises for example dispersant, wetting agent, hygroscopic salt, other salt, water-absorbing material and their mixture.
The preferred composition of the present invention comprises one or more other materials, and described other material is water-absorbing material.Preferred water-absorbing material is molecular sieve.Molecular sieve has the open architecture in the hole of uniform-dimension, and hydrone can enter this structure and may remain in this structure.Molecular sieve can be made by aluminosilicate, clay, glass, charcoal or carbon.The aperture of preferred molecular sieve is 3 or 4 dusts.Molecular sieve provides with bead, granule or powder type.In sieve sample, the average particulate diameter of bead or granule is generally 1-5 millimeter, and the average particulate diameter of powder is less than 1 millimeter.To be considered to be non-meltability solid to molecular sieve in this article.Think while there is molecular sieve, molecular sieve is dispersed in described matrix.
Dispersant is amphiphilic compound.More stable while contacting with hydroaropic substance than it when a part for dispersant molecule contacts with lyophobic dust, more stable while contacting with lyophobic dust than it when the different piece of described dispersant molecule contacts with hydroaropic substance.For example, while wishing to disperse one or more hydroaropic substances (ii) in the continuous phase of one or more lyophobic dusts (i), may need to use one or more dispersants.Again for example, when hope disperses to seal the powder particle of compound in matrix, for example when the part and described powder particle contact gear ratio of dispersant molecule, it contacts more stable with described matrix, and when more stable while contacting with described powder particle than it when the different piece of described dispersant molecule contacts with described matrix, may need to use one or more dispersants.
In using the embodiment of one or more waxes, also preferably use one or more dispersants.
The composition that preferably comprises one or more infusibilities (high-melting) wetting agent (being that the fusing point of wetting agent is higher than 120 ℃).Preferred infusibility wetting agent is mineral salt.More preferably potassium acetate.
Some suitable infusibility wetting agents are the mineral salt simultaneously with hygroscopy.
Matrix of the present invention can characterize by hydrophilic index (" HI "), and hydrophilic index is defined as follows:
HI=20×(H/T)
H is that the gross weight of all hydroaropic substances (ii) adds the gross weight of all wetting agents and removes the weight of all volatility compound cyclopropenes and the weight of all molecule encapsulation agents of removal, and T is the gross weight sum that H adds all lyophobic dusts (i).In a preferred embodiment, the powder particle that is encapsulated in the volatility compound cyclopropene in molecule encapsulation agent meets one or more hydroaropic substance standards, but the amount of H does not comprise the weight of any volatility compound cyclopropene, and the amount of H does not comprise the weight of any molecule encapsulation agent.Preferably, HI is more than or equal to 0.35; More preferably greater than or equal 1; More preferably greater than or equal 3; More preferably greater than or equal 7.Preferably, HI is less than or equal to 16, is more preferably less than or equals 13.
The preferred composition of the present invention comprises one or more following combinations, optionally contains in all cases other composition:
Polyethylene glycol and potassium acetate and micro-crystallization wax that number-average molecular weight is greater than 3,000;
The hydrophilic copolymers of ethene and vinyl acetate and number-average molecular weight are less than or equal to 3,000 polyethylene glycol and stearic acid;
The hydrophilic copolymers of ethene and vinyl acetate and polyvinylpyrrolidone and number-average molecular weight are less than or equal to 3,000 polyethylene glycol and stearic acid;
The hydrophilic copolymers of ethene and vinyl acetate and cellulose and number-average molecular weight are less than or equal to 3,000 polyethylene glycol and stearic acid;
Number-average molecular weight is less than or equal to 3,000 polyethylene glycol and micro-crystallization wax and stearic acid; And
Polyethylene glycol and cellulose and potassium acetate and micro-crystallization wax that number-average molecular weight is greater than 3,000.
Composition of the present invention can be prepared by any method.Preferred method is melting mixing.The example of melting mixing program is as follows: some or all components are placed in container, are added to TMIX (higher than room temperature and higher than the temperature of 25 ℃).TMIX is selected so that one or more components in container are liquid.Stir the mixture of these components, add other component (if any), further stir the mixture of these components, then the mixture of these components is cooled to room temperature (0-30 ℃).In melting mixing method, two or more components can be mixed with each other before mixing with other component.Expection is along with the mixture of these components is cooled to room temperature from TMIX, and matrix as herein described will form continuous phase, and any component that is insoluble to so described matrix will be disperseed wherein.
Preferably, lyophobic dust (ii) is dissolved in separately in described matrix or is dispersed in described matrix.Preferably, do not have any mixture of hydroaropic substance or hydroaropic substance to form the independent phase that any dimension is more than or equal to 0.5mm.Preferably, do not have any mixture of hydroaropic substance or hydroaropic substance to form by the raceway groove of described matrix.Preferably, not have one of them be lyophobic dust to composition of the present invention mutually with another is two of the hydroaropic substance forms of continuous phases altogether mutually.
In composition of the present invention, a kind of component is that one or more that be encapsulated in that molecule seals volatility compound cyclopropene in compound are sealed compound.This compound of sealing provides with powder (being called " EC " powder herein) form conventionally.EC powder can optionally comprise other compound (except volatility compound cyclopropene and molecule are sealed other compound compound), for example, following one or more: water, one or more monose (for example dextrose), one or more disaccharides, one or more amino-acid salts or one or more are selected from the adjuvant of vegetable oil, wax, cellulose derivatives, carbohydrate, plasticizer or surfactant.Preferably, the weight of EC powder of take is benchmark, and in EC powder, the amount of volatility cyclopropylene is equal to or greater than 0.01 % by weight; More preferably be equal to or greater than 0.03 % by weight; More preferably be equal to or greater than 0.1 % by weight.Preferably, the weight of EC powder of take is benchmark, and in EC powder, the amount of volatility cyclopropylene is equal to or less than 10 % by weight; More preferably be equal to or less than 6 % by weight.
Preferably, the weight of composition of take is benchmark, and in the present composition, the amount of compound cyclopropene is equal to or greater than 0.01 % by weight; More preferably be equal to or greater than 0.03 % by weight; More preferably be equal to or greater than 0.1 % by weight.Preferably, the weight of composition of take is benchmark, and in the present composition, the amount of compound cyclopropene is equal to or less than 1 % by weight; More preferably be equal to or less than 0.5 % by weight; More preferably be equal to or less than 0.3 % by weight.
Composition of the present invention can be by any use in a variety of modes.In a preferred embodiment, the solid that preparation comprises the present composition.For example, the described composition of part can be shaped as solid matter.For this solid matter, some suitable shapes comprise for example plate-like, granule, film, rectangular solid and other shape.
Again for example, can on base material, form the layer of described composition.This layer can for example, form coating by applicating liquid by any painting method (brushing, sprawl (spread), spraying, dosage (metering) or other method) on base material.In some embodiments, the liquid being applied on described base material can comprise dissolving or be dispersed in the present composition in liquid flux or other liquid-carrier; Described solvent or the evaporation of other liquid-carrier, leave the present composition.In a preferred embodiment, the described liquid being applied on base material is the fluid forming by heating composition of the present invention.Expection is by cooling or remove solvent or other liquid-carrier or adopt the two described layer is solidified or described layer is solidified simultaneously.
On base material, form in the embodiment of composition layer of the present invention, no matter this layer by which kind of method forms, and can described composition be come into operation by removing this layer from base material or leaving this layer sticking on base material.
In a preferred embodiment, the solids content of the present composition is more than or equal to 80%, more preferably greater than or equal 90%.
In the present invention preferably applies, the solid that comprises the present composition is positioned at internal tank.Described solid can be a part for inner surface of container, or can adhere to or be connected in inner surface of container, or described solid can conjointly not be present in internal tank.Preferably, described container comprises one or more plants or plant part; More preferably, described container comprises one or more fruit or vegetables (after it is gathered in).Expect described plant or plant part by evaporation or metabolic processes or by the two, to described internal tank atmosphere, provide water vapour simultaneously.Expect that this water vapour can promote volatility compound cyclopropene to discharge from composition of the present invention.
In the embodiment that comprises one or more plants or plant part at internal tank, the compound cyclopropene amount (in microgram) that characterizes every liter of container volume is useful.Preferably, described amount is more than or equal to 1 micrograms per litre; More preferably greater than or equal 2 micrograms per litre; More preferably greater than or equal 5 micrograms per litre; More preferably greater than or equal 10 micrograms per litre.Preferably, described amount is less than or equal to 500 micrograms per litre; Be more preferably less than or equal 250 micrograms per litre; Be more preferably less than or equal 100 micrograms per litre; Be more preferably less than or equal 50 micrograms per litre.
In a preferred embodiment, described container blow-by, gas can pass in and out described container.To container, composition of the present invention and plant or plant part, can select, along with volatility cyclopropylene leaves that the present composition enters in internal tank atmosphere and volatility cyclopropylene leaves described container again and enters in external container atmosphere, the volatility cyclopropylene of desired concn is remained in container atmosphere.In container atmosphere, preferred volatility compound cyclopropene concentration is more than or equal to 50ppb (part/hundred very much, volatility cyclopropylene gas volume/atmosphere volume); More preferably greater than or equal 100ppb; More preferably greater than or equal 200ppb.In container atmosphere, preferred volatility compound cyclopropene concentration is less than or equal to 5,000ppb; Be more preferably less than or equal 2,000ppb; Be more preferably less than or equal 1,000ppb.
It is useful that plant or plant part are contacted with compound cyclopropene.Compound cyclopropene can hinder the ethene effect of plant or plant part.The multiple effect that ethene excites for store gather in plant or plant part is harmful to.In some embodiments, for example, contact ring propylene can extend the useful life of having gathered in fruit or plant.
Preferably, the container that comprises one or more fruit or plant and comprise the present composition is placed on described container and its content are remained on and be greater than 0 ℃ and be less than in the environment of temperature of 25 ℃.More preferably, described temperature is more than or equal to 1 ℃, more preferably greater than or equal 2 ℃.More preferably, described temperature is less than or equal to 10 ℃, is more preferably less than or equals 5 ℃.
Preferably, composition of the present invention keeps 1 day or the longer time together with one or more plants or plant part in container; More preferably 2 days or longer time; More preferably 4 days or longer time.Preferably, composition of the present invention keeps being less than or equal to 30 days together with one or more plants or plant part in container; Be more preferably less than or equal 14 days.
Below embodiments of the invention.
In the present invention, used following abbreviation:
Abbreviation Implication
aCD Alpha-cyclodextrin
1-MCP 1-methyl cyclopropene
In following examples, use these materials:
In following examples, " molten mixture " prepared in accordance with the following methods.Listed material mixes by mechanical agitation under approximately 80 ℃ of conditions.
Measure in such a way the release of 1-MCP.
In the bottle with diaphragm seal, test.By promoting pin through barrier film, periodically from space in bottle, remove air sample.By the 1-MCP concentration of gas chromatographic analysis air sample.In air, the amount of 1-MCP characterizes with the percentage (" % release ") of putting into the 1-MCP of bottle again.Monitor % and discharge temporal evolution (" # days " expression " number of days " herein).
Comparative examples A:
20mg powder 1 and 3ml water are had under 22 ℃ of conditions in the bottle of membrane cover and mixing.All 1-MCP discharge fast.
Comparative example B
Under 22 ℃ of conditions, in thering is the bottle of membrane cover, 20mg powder 1 is suspended in 3ml side's waterborne gauze (paper mesh).All 1-MCP discharge relatively rapidly.
Comparative example CA
Material blends is coated on paper with the thick layer of 0.5mm, and cooling.Remove a slice coolant, and under 22 ℃ of conditions, be suspended at the bottleneck of the bottle with membrane cover.At the bottom of bottle, place 3ml water.Do not comprise meltability hydrophilic compounds.The release of 1-MCP is undesirably slow.
Comparing embodiment CB
Repeat the experiment of comparing embodiment CA, difference is that the temperature of bottle in experimentation is 4 ℃.The release of 1-MCP is undesirably slow.
Comparative Example D
About 300mg material blends is placed on to open plastics and weighs in boat, and under 22 ℃ of conditions, be suspended at containing 30ml water and be equipped with the bottleneck of the 2200ml bottle of membrane cover.Do not use solid hydrophobic material.The release of 1-MCP is undesirably fast.
Comparative Example E
The molten mixture of preparing material, and cooling.About 500mg material blends is placed on to open plastics and weighs in boat, and under 22 ℃ of conditions, be suspended at containing 30ml water and be equipped with the bottleneck of the 2200ml bottle of membrane cover.Do not use meltability lyophobic dust.The release of 1-MCP is undesirably fast.
Embodiment 1A
With the molten mixture of the thick layer coating material of 0.5mm, and cooling.From described base material, remove the cooling base material of a slice, and under 22 ℃ of conditions, be suspended in the bottleneck of the bottle with membrane cover.At the bottom of bottle, place 3ml water.Result is progressively to discharge ideally.
Embodiment 1B
Repeat the experiment of embodiment 1A, difference is that the temperature of bottle in experimentation is 4 ℃.Result is progressively to discharge ideally.
Embodiment 2
By the molten mixture fusing of described material, mixing, cooling, 200mg is pressed into the dish of diameter 12.7mm.Described dish is suspended to the bottleneck of the bottle with membrane cover under 5 ℃ of conditions.At the bottom of bottle, place 3ml water.Result is progressively to discharge ideally.
Embodiment 3
By the molten mixture fusing of described material, mixing, cooling, 200mg is pressed into the dish of diameter 12.7mm.Described dish is suspended to the bottleneck of the bottle with membrane cover under 5 ℃ of conditions.At the bottom of bottle, place 3ml water.Result is progressively to discharge ideally.
Embodiment 4
By the mixture melt of described material, mixing, cooling, 200mg is pressed into the dish of diameter 12.7mm.Described dish is suspended to the bottleneck of the bottle with membrane cover under 5 ℃ of conditions.At the bottom of bottle, place 3ml water.Result is progressively to discharge ideally.
Embodiment 5
By the mixture melt of described material, mixing, cooling, 200mg is pressed into the dish of diameter 12.7mm.Described dish is suspended to the bottleneck of the bottle with membrane cover under 5 ℃ of conditions.At the bottom of bottle, place 3ml water.Result is progressively to discharge ideally.
Embodiment 6
By material blends fusing, by molten mixture with the thick layer of 0.5mm be coated on paper, cooling, the bottleneck that a slice is suspended to the bottle with membrane cover under 4 ℃ of conditions.At the bottom of bottle, place 3ml water.Result is progressively to discharge ideally.
Result
Time (my god) % discharges
1 18%
4 36%
8 65%
Embodiment 7
Material
% by weight Material Function
33.5% PEG 8000 Meltability hydrophily
2.5% Dispersant
34.6% Wax Meltability hydrophobicity
5.6% Molecular sieve Water imbibition
11.2% Potassium acetate Wetability
5.6% Cellulose Thickening and non-meltability hydrophily
5.6% Powder 1
By mixture melt, mixing, cooling, on paper, apply the layer that 0.5mm is thick.A part is suspended to the bottleneck of the bottle with membrane cover under 4 ℃ of conditions.At the bottom of bottle, place 3ml water.Result is progressively to discharge ideally.
Result:
Time (my god) % discharges
0.75 10%
1.75 20%
2.75 30%
5.75 40%

Claims (15)

1. a composition, it comprises:
(a) meltability solid matrix, it comprises:
(i) one or more lyophobic dusts, and
(ii) one or more hydroaropic substances, and
(b) one or more that are encapsulated in volatility compound cyclopropene in molecule encapsulation agent are sealed compound, described in seal compound and be distributed in described matrix;
Described one or more lyophobic dusts comprise micro-crystallization wax, and described one or more hydroaropic substances comprise polyethylene glycol and the potassium acetate that number-average molecular weight is greater than 3,000.
2. a composition, it comprises:
(a) meltability solid matrix, it comprises:
(i) one or more lyophobic dusts, and
(ii) one or more hydroaropic substances, and
(b) one or more that are encapsulated in volatility compound cyclopropene in molecule encapsulation agent are sealed compound, described in seal compound and be distributed in described matrix;
Described one or more lyophobic dusts comprise stearic acid, and described one or more hydroaropic substances comprise that the hydrophilic copolymers of ethene and vinyl acetate and number-average molecular weight are less than or equal to 3,000 polyethylene glycol.
3. a composition, it comprises:
(a) meltability solid matrix, it comprises:
(i) one or more lyophobic dusts, and
(ii) one or more hydroaropic substances, and
(b) one or more that are encapsulated in volatility compound cyclopropene in molecule encapsulation agent are sealed compound, described in seal compound and be distributed in described matrix;
Described one or more lyophobic dusts comprise stearic acid, and described one or more hydroaropic substances comprise that the hydrophilic copolymers of ethene and vinyl acetate and polyvinylpyrrolidone and number-average molecular weight are less than or equal to 3,000 polyethylene glycol.
4. a composition, it comprises:
(a) meltability solid matrix, it comprises:
(i) one or more lyophobic dusts, and
(ii) one or more hydroaropic substances, and
(b) one or more that are encapsulated in volatility compound cyclopropene in molecule encapsulation agent are sealed compound, described in seal compound and be distributed in described matrix;
Described one or more lyophobic dusts comprise stearic acid, and described one or more hydroaropic substances comprise that the hydrophilic copolymers of ethene and vinyl acetate and cellulose and number-average molecular weight are less than or equal to 3,000 polyethylene glycol.
5. a composition, it comprises:
(a) meltability solid matrix, it comprises:
(i) one or more lyophobic dusts, and
(ii) one or more hydroaropic substances, and
(b) one or more that are encapsulated in volatility compound cyclopropene in molecule encapsulation agent are sealed compound, described in seal compound and be distributed in described matrix;
Described one or more lyophobic dusts comprise micro-crystallization wax and stearic acid, and described one or more hydroaropic substances comprise that number-average molecular weight is less than or equal to 3,000 polyethylene glycol.
6. a composition, it comprises:
(a) meltability solid matrix, it comprises:
(i) one or more lyophobic dusts, and
(ii) one or more hydroaropic substances, and
(b) one or more that are encapsulated in volatility compound cyclopropene in molecule encapsulation agent are sealed compound, described in seal compound and be distributed in described matrix;
Described one or more lyophobic dusts comprise micro-crystallization wax, and described one or more hydroaropic substances comprise polyethylene glycol and cellulose and the potassium acetate that number-average molecular weight is greater than 3,000.
7. the composition as described in any one in claim 1-6, is characterized in that, is distributed with one or more water imbibition materials in described matrix.
8. the composition as described in any one in claim 1-6, is characterized in that, is distributed with one or more wetting agents, one or more hygroscopy materials or its mixture in described matrix.
9. the composition as described in any one in claim 1-6, is characterized in that, described matrix also comprises one or more dispersants.
10. the composition as described in any one in claim 1-6, is characterized in that, described volatility compound cyclopropene is 1-methyl cyclopropene.
11. compositions as described in any one in claim 1-6, is characterized in that, described molecule encapsulation agent is alpha-cyclodextrin.
12. compositions as described in any one in claim 1-6, is characterized in that, the weight of described composition of take is benchmark, and the amount of described volatility compound cyclopropene is 0.01-1 % by weight.
13. 1 kinds of methods of processing plant or plant part, it comprises the composition described in any one in described plant or plant part and claim 1-12 is placed in container, and make described plant or plant part with together with composition as described in any one in as claim 1-12 as described in keep 1 day or the longer time in container.
14. methods as claimed in claim 13, is characterized in that, described volatility compound cyclopropene is 1-methyl cyclopropene, and described molecule encapsulation agent is alpha-cyclodextrin.
15. methods as claimed in claim 14, is characterized in that, the amount that is placed on the 1-methyl cyclopropene in described container is 1 micrograms per litre-500 micrograms per litre.
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Families Citing this family (17)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
KR101487115B1 (en) 2010-11-12 2015-01-28 가부시키가이샤 고베 세이코쇼 Gel reducing device and gel reducing method
US10182567B2 (en) 2011-03-27 2019-01-22 Cellresin Technologies, Llc Cyclodextrin compositions, articles, and methods
CA2831213C (en) 2011-03-27 2016-05-17 Cellresin Technologies, Llc Cyclodextrin compositions, articles, and methods
TW201400023A (en) * 2012-06-20 2014-01-01 Agrofresh Inc Particle size reduction
RU2015114260A (en) * 2012-09-17 2016-11-10 Агрофреш Инк. COMPOSITIONS AND METHODS FOR DOUBLE VACUUM COMPOUND CAPSULATION
AU2013302242B2 (en) * 2012-11-30 2014-07-24 Kimberly-Clark Worldwide, Inc. Controlled release compositions and methods of using
AU2014227556B2 (en) * 2012-11-30 2016-09-15 Kimberly-Clark Worldwide, Inc. Controlled Release Compositions and Methods of Using
US9320288B2 (en) 2012-11-30 2016-04-26 Cellresin Technologies, Llc Controlled release compositions and methods of using
BR112015018619A2 (en) * 2013-02-08 2017-07-18 Agrofresh Inc dry cast coating process and formulation for volatile compounds
US9421793B2 (en) 2014-06-26 2016-08-23 Cellresin Technologies, Llc Electrostatic printing of cyclodextrin compositions
CN105437676B (en) * 2014-08-14 2020-03-24 上海利统生化制品有限公司 Laminate for blocking ethylene reaction of plant and preparation method thereof
KR101697423B1 (en) 2015-04-07 2017-01-18 한국기술교육대학교 산학협력단 Dome connector for easy assembling and structural rigidity
CR20230013A (en) * 2016-02-19 2023-05-22 Hazel Tech Inc Compositions for controlled release of active ingredients and methods of making same
EP3784038A1 (en) 2018-04-27 2021-03-03 Fresh Inset S.A. Compositions and articles comprising complexes of 1-methylcycloproprene and alpha-cyclodextrin
BR112022015315A2 (en) 2020-02-03 2022-09-27 Fresh Inset S A STABLE COMPOSITIONS OF 1-METHYLCYLOPROPENE AND USES THEREOF
WO2023288294A1 (en) 2021-07-16 2023-01-19 Novozymes A/S Compositions and methods for improving the rainfastness of proteins on plant surfaces
WO2023225459A2 (en) 2022-05-14 2023-11-23 Novozymes A/S Compositions and methods for preventing, treating, supressing and/or eliminating phytopathogenic infestations and infections

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313770A (en) * 1998-02-09 2001-09-19 西南研究院 Silicate-containing powders providing controlled, sustained gas release
CN1346594A (en) * 2000-09-29 2002-05-01 罗姆和哈斯公司 System for delivery of low water demand cyclopropene
CN1371603A (en) * 2001-02-26 2002-10-02 罗姆和哈斯公司 Cyclopropene supply system
CN1440649A (en) * 2002-02-27 2003-09-10 罗姆和哈斯公司 Supply system of cyclopropenyl compound
CN1457636A (en) * 2002-05-14 2003-11-26 罗姆和哈斯公司 Method and device for producing cyclopropenyl compound

Family Cites Families (21)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5518988A (en) 1994-06-03 1996-05-21 North Carolina State University Method of counteracting an ethylene response in plants
US5914120A (en) * 1995-06-05 1999-06-22 Southwest Research Institute Amine-containing biocidal compositions containing a stabilized chlorite source
US6452060B2 (en) * 2000-04-11 2002-09-17 Rohm And Haas Company Method to prepare cyclopropenes
US6444619B1 (en) * 2000-09-28 2002-09-03 Rohm And Haas Company Delivery system for cyclopropenes
US6953540B2 (en) * 2000-09-29 2005-10-11 Rohm And Haas Company Continuous process for the preparation of encapsulated cyclopropenes
US6762153B2 (en) * 2001-10-18 2004-07-13 Rohm And Haas Company Delivery system for cyclopropenes
US6770600B1 (en) * 2003-02-28 2004-08-03 Rohm And Haas Company Delivery systems for cyclopropene compounds
US7041625B2 (en) * 2003-08-21 2006-05-09 Rohm And Haas Company Method to inhibit ethylene responses in plants
CA2504840C (en) * 2004-05-05 2008-03-18 Rohm And Haas Company Humidity activated delivery systems for cyclopropenes
TW200603731A (en) * 2004-05-19 2006-02-01 Rohm & Haas Compositions with cyclopropenes and metal-complexing agents
EP1609359A3 (en) 2004-06-24 2011-10-05 Rohm and Haas Company A method for treating plants or plant parts
WO2006072180A1 (en) * 2005-01-10 2006-07-13 Her Majesty The Queen In Right Of Canada As Represented By The Minister Of Agriculture And Agri-Food Compositions and methods to improve the storage quality of packaged plants
US20070117720A1 (en) * 2005-11-18 2007-05-24 Jacobson Richard M Compositions with cyclopropenes
KR100823872B1 (en) * 2005-11-18 2008-04-21 유상구 Cyclopropenes-generating Devices to Control Ripening Processes of Agricultural Products
US20070265167A1 (en) * 2006-05-15 2007-11-15 Todd Edgington Treating horticultural crops
US8691728B2 (en) * 2006-11-09 2014-04-08 Rohm And Haas Company Cyclopropene compositions
JP5128392B2 (en) * 2007-08-03 2013-01-23 ローム アンド ハース カンパニー Oil blend
ES2371603T3 (en) * 2008-08-25 2012-01-05 Rohm And Haas Company TREATMENT OF BANANA.
CA2692211C (en) * 2009-12-14 2011-09-13 Cellresin Technologies, Llc Maturation or ripening inhibitor release from polymer, fiber, film, sheet or packaging
CN102892298A (en) * 2009-12-28 2013-01-23 罗门哈斯公司 Method of handling bananas
ES2695578T3 (en) * 2011-06-29 2019-01-09 Agrofresh Inc Method for handling mangoes

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1313770A (en) * 1998-02-09 2001-09-19 西南研究院 Silicate-containing powders providing controlled, sustained gas release
CN1346594A (en) * 2000-09-29 2002-05-01 罗姆和哈斯公司 System for delivery of low water demand cyclopropene
CN1371603A (en) * 2001-02-26 2002-10-02 罗姆和哈斯公司 Cyclopropene supply system
CN1440649A (en) * 2002-02-27 2003-09-10 罗姆和哈斯公司 Supply system of cyclopropenyl compound
CN1457636A (en) * 2002-05-14 2003-11-26 罗姆和哈斯公司 Method and device for producing cyclopropenyl compound
US20030220201A1 (en) * 2002-05-14 2003-11-27 Kostansek Edward Charles Method and device for the generation of cyclopropene compounds

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